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Hydrodewaxing catalyst, preparation method and application thereof

A hydrogenation dewaxing and catalyst technology, applied in molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems of paraffin selectivity reduction, molecular sieve skeleton collapse, catalyst reduction, etc., and achieve low cracking capacity , reduce side reactions, high catalytic activity effect

Active Publication Date: 2012-05-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method adopts the method of high-temperature roasting catalyst support to reduce the acidity of the catalyst, and its main disadvantage is that the aluminum atoms on the outer surface of the molecular sieve cannot be selectively removed during the high-temperature roasting dealumination process, thereby affecting the improvement of the selectivity of the catalyst, and dealumination When the degree is deep, it will also cause the collapse of the molecular sieve framework, which will reduce the selectivity of paraffins.

Method used

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  • Hydrodewaxing catalyst, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) made of binder added to HZSM-5 molecular sieve (SiO 2 / Al 2 o 3 Molar ratio 38) and hydrogen type β molecular sieve (Si / Al molar ratio 26, specific surface area is 420m 2 / g, with a relative crystallinity of 90%), mixed uniformly, extruded, dried at 130°C for 4 hours, and calcined at 580°C for 4 hours to obtain a carrier.

[0031] The above-mentioned carrier is added to an aqueous magnesium nitrate solution with a magnesium oxide content of 5 wt% and impregnated by equal volume for 5 hours. After filtering, the obtained solid phase is dried at 120° C. for 4 hours to obtain a magnesium-modified carrier.

[0032] Add cyclohexane to dimethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 15 wt%, and then add the magnesium-modified carrier to the above-mentioned silicone oil-organic mixed solution to immerse in an equal v...

Embodiment 2

[0035] Will be made of small hole alumina (specific surface 238m 2 g -1 , pore volume 0.48mL·g -1 ) was added to the mixture of HSM-5 molecular sieve and hydrogen-type β molecular sieve (same as Example 1), kneaded evenly, extruded, then dried at 130°C for 4 hours, and roasted at 580°C for 4 hours. Get the carrier.

[0036] The above-mentioned carrier is added to an aqueous solution with a calcium oxide content of 6wt% calcium nitrate and impregnated at a volume ratio of 1:1.5. The impregnation time is 4 hours. After filtering, the obtained solid phase is dried at 100°C for 5 hours to obtain calcium-modified carrier.

[0037] Add solvent gasoline to ethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 20 wt%, and then add the calcium-modified carrier to the above-mentioned silicone oil-organic mixed solution for immersion at a volume ratio of 1:1.5, and the immersion time for 3 hours. After filtration, it was drie...

Embodiment 3

[0040] The preparation of the carrier is the same as in Example 1.

[0041] The above-mentioned support was added to an aqueous zinc nitrate solution with a zinc oxide weight content of 6 wt% and impregnated by equal volume for 5 hours. After filtering, the obtained solid phase was dried at 120° C. for 4 hours to obtain a zinc-modified support.

[0042] Add xylene to phenylmethyl silicone oil to obtain a silicone oil-organic mixed solution with a silicon oxide weight concentration of 18%, and then add the zinc-modified carrier to the above-mentioned silicone oil-organic mixed solution for impregnation at a volume ratio of 1:2. The time is 3 hours. After filtration, it was dried at 100° C. for 4 hours and calcined at 580° C. for 4 hours to obtain a zinc-silicon-modified carrier S3, wherein the zinc oxide weight content was 2.0%, and the silicon oxide surface coating content was 5.0 wt%.

[0043] The obtained carrier S3 was immersed in an aqueous solution containing nickel and ...

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Abstract

The invention discloses a hydrodewaxing catalyst, a preparation method and application thereof. The hydrodewaxing catalyst employs a carrier modified by metal auxiliary agent and silicon. First, a carrier is loaded with metal auxiliary agent by an immersion method; then the carrier is modified by silicone oil to form a silicon oxide coating thereon. The method can effectively adjust acidity of an interior surface and an outside surface of a molecular sieve and the pore shape, so as to facilitate wax molecules to diffuse into tunnels of the molecular sieve and carry out a shape selective cracking reaction and an isomerization reaction; the method has high catalytic activity and selectivity on object product; and as weak acidity of the outside surface and low cracking capability of the molecular sieve, side reactions of the object product are reduced. The hydrodewaxing catalyst is suitable for a hydrodewaxing process of a wax-containing raw material, especially a hydrodewaxing process of diesel oil or lubricating oil.

Description

technical field [0001] The invention relates to a hydrogenation dewaxing catalyst and a preparation method thereof. The catalyst is used in the hydrodewaxing process of waxy hydrocarbon raw materials, especially in the hydrodewaxing process of diesel oil or lubricating oil. Background technique [0002] Hydrodewaxing refers to the reduction of the waxy molecular content of a waxy hydrocarbon feedstock on the surface of a suitable catalyst in the presence of hydrogen. The principle of dewaxing is that under certain operating conditions, the raw material is mixed with hydrogen and contacted with a hydrodewaxing catalyst. High freezing point components such as aromatics are selectively cracked into small molecules, while other components are basically unchanged, and the purpose of lowering the freezing point of the oil is finally achieved. See US3,894,438, US3,894,439, US 4,173,148 for the specific catalytic dewaxing process. Diesel hydrodewaxing is generally called diesel h...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/80C10G73/02C10G45/64
Inventor 李永泰孟祥兰高鹏
Owner CHINA PETROLEUM & CHEM CORP
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